Acyclic hydrazinium salts



United States Patent 2, 67 ACYGLIC SALTS Bernard Rudner, Silver Spring, Md., assignor to'W. R.

Grace 8: Co., New York, N.Y,, a corporation of Connecticut r No Drawing. Application October 29,1957

ria 2 2 I 11 Claims. (Cl. 260-569) This invention relates to quaternary nitrogenous salts. In one specific aspect, it relates to quaternized derivatives of substitutedhydrazines. In still another aspect, it

relates to novel acyclic fatty oxyalkyland polyoxyalkylhydrazinium salts.

Heretofore, quaternary hydrazinium salts have been obtained on only a laboratory scale. A known preparation of these interesting compounds comprises the reaction of 1,1-disubstituted hydrazines with alkylating agents, e.g. methyl chloride. Because of the extreme difliculties involved in preparing the parent hydrazines and the limitations of their final alkylation (see 0. Westphal, Berichte der Deutschen Chemischen Gesellschaft, 74: 759 et. seq., 1365 et. seq. (1941) only limited types of hydrazinium chlorides have been heretofore available. Using Westphals method it is obvious that the preparation of any specific hydrazinium cation depends upon the availability of the. substituted hydrazine, as Well as the ablity of that substituted hydrazine to undergo alkylation with the necessary alkyl halide. Among the compounds discovered by Westphal were the vtrihexylhydlazinium chloride, the dodecyldimethylhydra zinium chloride, the hexadecyl- :dimethylhydrazinium bromide and the ,hexadecyldirnethylhydrazinium iodide. Because of the inherent limitation of his alkylation reaction, Wesphal found it impossible to prepare hydrazinipmchlorides of greater chain length than the doceyldimethylhydraziniumsalt. He was more successful using methyl bromide and methyl iodide as alkylating agents; however, he did not prepare hydra- .zinium salts having a carbon chain longer than 16 carbon atoms. Since long chain alkyl substituted hydrazinesarelnot readily available,.the only known compounds of this particular type' are those prepared by Westphal. We have discovered certain distinctly different acyclic hydrazinium salts-which vary. bothin their. structure and in their utility from the compounds of Westphal; .The vast utility of our novel acyclic hydrazinium salts will be discussed in detail infra. This applicationgis a continuation-in-part of my copending application S.N. 641,810, :filed February 25, 1957.

It is, therefore, an object of the present invention to provide a new generic class of acyclic hydrazinium salts which, because of their unique properties and utility, are commercially acceptable as dye, detergenLphamaceutical and resin intermediates as well as for a variety of other purposes.

' In accordance with the present invention we have made available a new generic class of useful hydrazinium chlorides having the formulaz 2,909,567 Patented Oct. 20, 1959 dienyl radicals fitting this description. R" may also be a benzyl or halobenzyl radical. ,A is halide, sulfate, phosphate, nitrate or lower allranoate.

It has recently been discovered that chloramine will react with tertiary amines to'form 1,1,1-trisubstituted 'hy- This new reaction presents practidrazinium chlorides. cally limitless possibilities for'the preparation of novel and interesting chemical compounds, which, because of" their structure and inherent physical properties, have a wide range of uses. Tertiary amines are readily available bases. Chloramine is an excellent reagent since it x can be economically obtained in commercial quantities by using the well known process of Harry H. 'Sisler et al.,

described in U.S. Patent No. 2,710,248 where chlorine and ammonia are reacted in the vapor phase to produce chloramine (moriochloramine)! By treating a particular'class of tertiary -mines having a structure which is embraced by the general formula supra, with chloramine, we have discovered the new generic class of hydraainiuin" chlorides referred to hereabove. The corresponding salts of the presentinvention are preparable by metathesis.

in making the chloride compounds of the present inventionit is ually suitable to contact chloramine with a solution of the selected tertiary amine, allow the reaction to proceed untiltlie desired quantity of chloramine is consumed and then same and purify the resultant hydrachloride by standard "laboratory techniques. While chloramine is most advantageously prepared in the form of'a gaseous chloraminerammonia-nitrogen stream obtained from a generator constructed according to the teachings of Sisleret al.,other n ethods are equally adaptinlnorganic Syntheses, vol. I, 59 (1939). Alternately,-

the compounds of the presentwinvention can be made directly by the procedure described in the copending application of :Bernard Rudner, vSerial No. 605,230, filed August 20, 1 956, which teaches the reaction of chlorine,

ammonia an d the tertiary amine in the presence of excess ammonia. For simplicity, when both the amine and the product aresoluble in the same inert solvent, we have found the Rudner method to be a preferred technique.

Tertiary amines suitable for'the'purpos'e of thepr'esent invention areshown hereunder, in .Table I. .These sug- -.gested amines areinteiided merely to be illustrative, since it is obvious that the lio'mologs of these compounds ernbraced by the general formula set'forth above would be equally applicable in the production of individual species of our new andnovel class. V

TABLE I Parent amine Product hydrazinlum Salt Octyldiethannlmninn Di(2ethylhexyl) othm-mlamine Dinonylaminopropmnl ecyliminobis-(tbutanol) Undecenyldiethannlaminp N (2,4,4,6,6 pentamethylheptyl 2) N methylhydroxy ethylamine. Dodecyliminobis (2propanol) Didodecylethanolamine Dilauryleth'm nlamine Diterradecylaminopropanol Pentadecenyliminobisethanol. Cetylmethylhydroxybutylamine- Octadecenyldiisopropanolamine Dioctadecylaminoethnno] Dodecyliminobis (2-hydroxyethoxyethane) Dihexadecylhydroxy (tetraethoxy) ethylamme Methyloctyl (.Lhydroxvethyl) amine Z-ethylhexylimino-bis-(3-propanol) Hexadecylimino-bis- (tetra-irpropoxy-2propanol) Methyltetracosanyl (hydroxytetradecaethoxyethyl) 31111116 Octadienylimino-bis'tetradecaethoxyethanoL N benzyl N 2,3 dihydroxypropyl N 2 methylpenta- 1, l-bis-(i'rhydroxyethyl)-1-n-octylhydrazinium chloride.

1, 1-bis-(2-ethylhexyl)-1 (2hydroxyethyl) hydrazmium chloride.

1,1-bis-n-nonyl-l-(ii-hydroxypropyl) hydrazinium chloride.

1,1-bis-(4-hydroxybutyl)-1-deey1hydrazinium chloride.

1,1-bis-(2-hydroxyethyl)-1-(10-undecenyl) hydrazinium chloride.

1 1(121,4, 46,6 pentamethylheptyl 2) 1 (2 hydroxyethyl) 1 methylhydrazinlum on e c l-dodeeyl-l,l-bis-(Z-hydroxypropyl) hydrazinium chloride. 1,1-didodecyl-1-(thydroxyethyl) hydrazinium chloride,

decylarnine. Octadecadienyl bis (hydroxytetracosanethoxyethyl) amine.

. 1,1 bis (hydroxytetracosanethoxyethyl) l octadecadienyDhydrazinium chloride 3,5-dichlorobenzyloctylhydroxyethylamhie- 1-(3,5 dichlorobenzyl) -1-oct;yl -1-(2-hydroxyethyl) hydrazinium chloride.

The amines set forth in Table I, supra, may be divided into two general types; viz: 1) those synthetically derived from fats and (2) those synthetically derived from lower olefins (petrochemicals).

Type 1 amines are prepared as follows: naturally occurring fatty glycerides are hydrolyzed to acyclic acids RCOOH, where R is a paraflinic or olefinic residue having from 7 to 21 carbon atoms. These acids are treated with ammonia in the presence of a catalyst to give a cyanide RCN, often by way of amide formation. This product is hydrogenated catalytically to convert the cyanide to a mixture containing primary and secondary amines plus some tertiary amine. The primary and secondary amines thus formed are further alkylated as discussed below. It is noteworthy that thefatty amines are often obtained as mixtures. The coconut oil fatty acyclic residue is 8% octyl, 9% decyl, 47% dod ecyl, 18% tetrodecyl, 8% hexadecyl, octadecyl, 5% octadecenyl; the soy residue is hexadecyl, 10% octadecyl, 35%

They are generally manufactured by the reaction of ethylene oxide and propyleneoxide on the primary and secondary amines whose preparation was described above.

octadecenyl, octadecadienyl; tallow is 30% hexadecyl, 25% octadecyl, 45 octadecenyl. It is, of course, possible by fractional distillation or other procedures to get nearly pure homologues from these fatty amine mixtures. The fatty amines may also be hydrogenated to convert them to mixed alkyl residues substantially free of unsaturated compounds.

The second general type of amine is often prepared as follows: propylene, butylene, isobutylene, can be dimerized, trimerized, etc., and the resulting olefinic mixture may be condensed with e.g. urea, ammonia, hydrogen cyanide or amines to give eventually primary or secondary amines which are further alkylated to the tertiary amine as discussed below. Polymerization of the lower olefin gives a mixture of branched chain alkenes of varying degrees of polymerization. This combined with the isomerization due to several possible locations of the final double bond accounts for the fact that commercial products are usually mixtures of amines. Branched chain amines are more oil soluble and less water soluble than RRNCH OHzOH na'iwcmcmoorncmon etc Customarily, oxyalkylation is done to a fixed epoxideamine molar ratio. But oxiranes are highly reactive and 'the reaction cannot be controlled to give exclusively the desired product. Even when the alkyl chains (R and R) are derived from a single component, oxyalkylation gives a multiplicity of products. A detailed example will be helpful. When one mol of pure n-C H NH takes up 13 mols of C H O, the average structure iz za u a i he ia (chemically impossible) can be written for the product. What actually results is a complex mixture. of

(31 2 n zH4 (0211.0).11 where x and z can have any value but their overall sums must average 13 (the number of mols of C H O taken up). Thus a graph of the sums of x-l-y will follow a Boltzmann distribution curve when plottedagainst the amount of a given species present in the reaction mixture.

Percent given species in reaethe corresponding fatty or unbranched amines. A typical tion mixture process is outlined below: V

HCN (CHX)IC=CH: CH;[(CH )3C-CHfl -C=CH H2O a[( s)z (--C z)2 NHCHO 7 CHr.(ymhcn'olqflnqyPom):3 HC'OZH Such a mixture is not .commerciallyresolvable but is re- I 1 l r ferred to as if it were a single species. For example,

Tertiary amines suitable as starting materials fo r the practice of this invention are commercially available.

the manufacturer might well call the above ethoxylated amine, BA 12/ 13, where 12'is the average length of R in the alkyl and 13 the mols of C H O taken up.

out a H nomoNnwncimo nonirnwlmoain Ha ,Q iJ' The remaining amine hydrogen is still available for alkylation by other techniques; the resultant tertiary amines are also useful as starting materials in the practice ofmy novel invention.

CH3 CH3 RCHECN' on, Cha on 7' CHzO HO 02H CH 3 \gioomonici RCHzCN v on, canon These amines are still sterically hindered and. react slowly with chlorarnine. I

In discussingthe several methods by which chloramine may be made available for reaction with the tertiary amine, we indicate choice of the reaction medium could be varied extensively. We have successfully obtained our novel compounds by conducting the reaction of chloramine and the appropriate tertiary amine in anhydrous solution using as a solvent either an excess of the reactant amine or an unreactive organic liquid. The reaction may also be carried'out in aqueous solution if such conditions appear to be preferable. The term unreactive as applied to the organic liquid solvent is intended to embrace those solvents that donot react preferentially with chloramine, ammonia or the. reactant amine under the conditions. employed. It is obvious, therefore, that the choice of solvent is one of economy, and simplicity. For goodabso'rption'tand, therefore reaction) it may be desirable to. bubble chloramine through a long column of solution comprising .a tertiary amine dissolved in a relatively cheap inert: solvent. Sol-. vents which serve this purpose include hydrocarbons, e.g. heptane, cyclohexane, benzene, xylene andfthe like; ethers, e.g. diethyl ether, diamyl ether, dioxane anisole; amides, e.g. dimethylformamide and dimethylacetamide; halohydrocarbons, e.g. chloroform, carbon tetrachloride, trichloroethylene, trichlorobenzene; and nitroaromatics, itrobe s e. r pe i l p rpo eswater nd othe hydr ylics v n s uch as han l. nd: 2- thoxye hano m y' eu ed; 1. e

The no el Salts; t er h n; h or e) o the. n t nt. invention aregpreferlabgly, but, by no, means; necessarily, prepared by the metatheticalv reaction between: the hy-.- drazinium chloride and an=alkali metalsaltofithe desired anion. In short, the methodcornprises mixing aqueous before conversio'ntoth'e requiredjsalt. It may bedesirable' to convert the halide salt to the hydroxide with moist silver oxide; neutralization with an acid gives the hydrazinium salt of that acid free of extraneous anions.

Because of the balanced interplay of polar and nonpolar groupings, my novel compounds have general surfactant properties. Salts with 1-5 ethylene oxide residues have good emulsifying properties. For example, very good oil-in-water emulsions are obtained with ke'rosene; excellent water-in-oil emulsions result with mineral or soybean oil, which may be used as anti-static wool lubricants. The hydrophile-lipophile balance is modified by the addition of ethylene oxide residues. When less ethylene oxide is present in the compound, water-in-oilv emulsions are favored and less chance-of salting out of the emulsion is possible (40% oil, 10% emulsifier and 50%. water constitute, one such formulation). Unlike the amine acetates, these salts are not alkali sensitive and can, therefore, be used in paint stripping formulations. Tallow-bis-hydroxypolyethoxyethylhydrazinium chloride, aqueous sodium hydroxide and a solvent like Cellosolvewould constitute such a formulation. Not only do these salts have the power to emulsify oily materials but they are capable of peptizing-aggregates of solid particles. The increased amount of oxygen present in the molecule as compared to the more aliphatic hydrazinium salts of my copending applications, S.N. 641,271 and- S.N. 641,810, decreases the softening power and antibacterial properties of the compounds. The presence of ethereal oxygen has other advantages which will be illustrated below. As expected, the presence of ethoxy groups increases both the water solubility and water dispersability of the oxyalkylhydrazinium salts.

My novel compounds produce brightly colored dye stuffs when treated withaqueous solutions of acid dyes (i.e. those. substances containing sulfonic, carboxylic or other acid groups). The resulting products, the hydrazinium salts of the acid dyes, vary in physical properties with the chain length of the R group and the particular dye used. Products ranging from solvent-soluble dyes to insoluble pigments have been prepared in this manner. Saturated long-chain hydrazinium salts of instant invention having a minimum number of hydroxyl groups, in general, form water-insoluble solvent-soluble salts useful in dopes, lacquers and in ballpoint pen ink. In the latter case, the hydrazinium portion of the molecule apparently functions to promote the smooth flow of ink and cleanliness of the nub. Certain salts, are exceptionally useful in making flushed pigments (where wet pigment filter cake is simultaneously freed of Water and dispersed in the oil matrix to be used by the printer). When Peacock blue is made by the standard process of laking Neptune blue (Color Index No. 671) with barium chloride on freshly precipitated alumina, it is less readily flushed than a similar preparation containing less than' 5% by weight of l,l-bis-(2-h'ydroxyethyl)-l-octadecyl hydrazinium chloride.

Since the novel, hydrazinium salts possess considerable. anti-oxidant power as well as affinity for metals, they form emulsions which are particularly useful as cutting oil additives for machine-shop work. The products also exhibit added utility when used in electroplating processes. For instance, the addition of a small amount of any ofmy acid insensitive salts to an electroplating solution results in a depositionof a clearer, brighter more coherent covering filmon the electroplated object. a Moreover, my compounds 'are excellent dispersing agents for Water; insoluble components'in, electroplating. My compounds are also good additives for froth flotationagents In general,"frothiilotation agents do not possess goodv wettinglouttyi'z; surfactant characteristics). The addi tion of any onejof my novel compounds to such an agent; greatly enhances its ability vt'o.;Wet the, surfaces of the; aii bubbles formed during froth'fiotation. This effect. is. attributed to-thepresence of ether'linkages and hydroxyl, 5 groups" in my. novel compounds.

,7 The scope and utility of my invention is further illustrated by the following examples:

Example I A chloramine generator was constructed according to the teachings of Sisler et al., supra.- The generator consists of a horizontal Erlenmeyer flask, the bottom of which contains an outlet tube which is directed into'the reactor containing liquid tertiary amine. 'Amm'onia and chlorine (which may be diluted with nitrQgenYare inQ troduced separately into the top of the flask through concentric conduits. chloramine and ammonium chloride are formed in the flask at the point where the chlorine and ammonia vapors come into contact; [A rod is provided in the chlorine inlet stream to prevent-any' 'plu'gging of that stream with ammonium chloride. The out let end of the flask is masked with glasswool to collect any ammonium chloride particles which otherwise would beca'rried into the reaction mixture. The chloramine yield for any one set of gas flow meter readings is determined by removing the reactor and generating the chloramine directly'into a series of three chilled traps. Under the conditions of chloramine generation, (only ammonia, chloramine, and nitrogen can pass through the glass wool into the traps. Since the traps 'a remaintained at at least 70 C., the ammonia and chloramine condense therein and react relatively slowly (compared to the chlorine-ammonia reaction velocity) td form nitrogen, possibly hydrazine and ammonium chloride. By allowing the low temperature condensate to come to room temperature slowly, the chloramine is'fconverted quantitatively to non-volatile (at 30 C.) ammonium chloride, while the volatile bases escape by volatilization. Therefore titration of the white residue (obtained on evaporation of the condensate) for chloride gives a direct measure of the chloramine generated. This can be related back to a measure of the chlorine used to obtain the chloramine yield. There 'is an alternate procedure which is suitable for use when chloramine is actually being consumed by reaction with a tertiary amine- The amount of chlorine used in a run, which is the-limiting reagent quantity for yield calculation, can be measured directly, e.g., by weight of the chlorine cylinder before and after use, or by use of flow meters. The amount of ammonium chloride retained within the" generator is' determinable by titrating an aliquot of the aqueous solution of all of the solid remaining within the chloramine generator after the reaction has been completed. The chloramine yield, expressed as percent of the theoretical, yield, can then be calculated from the formula:

(AB)200 A where A is the total number of mols of chlorine passed into the generator and B is the number of equivalents of chloride retained within the generator." The chloride content of the generator thus serves as an indicator of chloramine efficiency.

Percent:

Example II An amine which is largely octadecylimino-bis-ethanol C H N(C H OH) is available commercially-under the trade-name Ethomeen 18/ 12. It is a cream-colored brittle wax soluble in'isopropyl alcohol, benzeneand chloroform but not very soluble in hexane. The manufacturer states that the amine has an average molecular. weight of 372 suggesting a purity of roughly 95% 8 ride. 'Evaporation of' theicle'ar filtrate gave 22 g; of a residue containing 7.5% Cl and was a :15 mixture of product tostarting amine. The initial precipitate was extracted with hot chloroform, the extract'evaporated and the residue washed with hot ethyl acetate. There resulted 7 g. of a white crystalline solid containing 8.7% CI- (theory 18.69). ;A similar hot ethyl acetate washing of the 22 g. residue from the reaction filtrate gave 15 g. of a white solid containing 8.5% CI-. The combined pure productdissolves in water with some foaming and is partially soluble in xylene...

CmH NwiEOHh-I- CINE} [C aH37N(CgH OH)g Cl" Example III A chlorarnine-anlmoIiia gaseous mixture was bubbled into a trichloroethylene solution of tallow-bis-hydroxypolyethoxyethylamine, a product known commercially as Ethomeen T/ 25 The parent amine is represented by its manufacturer as having the structure:

(OQH40):'H

(G2H4O)1IH wherein x+y averages 15. The compound has an average molecular weight of -937. R represents tallow, a

mixture of fatty moieties previously described and-the compound has an average molecular weight of 937. A white precipitate formed inthe reaction mixture as the reaction progressed. Extraction of this'precipitate with ethanol, gavefine, transparent, off-white prisms of tallowbis-hydroxypolyethoxyethylhydrazinium chloride, which melted at198-201 C. and decomposed at 2l8233 C.

Example IV A eommercial mixture similar to that of Example III known as Ethomeen S/25is a mixture of homologs of the general formula: V

In the formula, R is a fatty hydrocarbon residue derived from soybean oil containing a mixture of hexadecyl, octadecyl, o'ctadecenyl, and octadecadienylchainsas previously described in the specification. In this product x+y can vary from 2 to at least 25 and has an average of 15. Ethomeen S/ 25 has an experimentally determined neutralization equivalent of 939. Four. batches of 200 g'. of this amine mixture were each dissolved in 1000 ml. of xylene- The resulting solutions were subjected to a chloramine stream of 0.004 mol per minute from the generator for a period of 60 minutes. They were filtered and the filtrates were combined and resplit into three portions. Each of these solutions were again subjected tochlo'ramination. They were refiltered and rechloraminated, refiltered andthe filtrates were evaporated to dryness in a vacuum to give 875 g. of a wet paste. This material wasvacuum dried at about 47 C. for 24 hours to'give 765.9 g. of about 97% pure 1,1-bis-[2-(hydroxysesquixpentaethoxy)ethyl]-1-soyhydrazinium chloride as a viscous white amber oil. in water and also soluble in xylene.

. k Example V V Kcommercial product similar to that described in Example IV marketed, as Ethomeen 18/60 is described by i meag e a b ri he u u 'mv womcnn...

- cred s} r wherein] x+'y'=js'o,jgaad R 'is deriv ed, from commercial stearic; d, largely'C li 'with'about 6% CHI-I33 and This oil was very soluble Physically, this product is hard wax with a greasy feel. It was readily soluble in water with considerable foaming. In addition, it was found to be soluble in most of the common solvents except p'arafiins. The wax was sub jected to heat which caused it to soften and run at 180 C.

and decompose above 208 C. The novel product formed.

a water insoluble hexafiuorophosphate melting from 50-55 C. Example V1 Since the Ethomeens are steadily water soluble, they can be converted into hydrazinium chlorides in aqueous solution. While this procedure appears to offer no particular advantage, per se, it is demonstrative of the flexibility of the chloramine-tertiary amine reaction. Aqueous chloramine, prepared according to the procedure.

of R. A. Coleman (US. Patent No. 2,404,695) was added to 0.5 g. of Ethomeen 18/60 in 10 ml. of ice water using three equivalents of titrable chloramine to one of the amine. The reaction mixture was allowed to stand overnight at 5 C. The resultant clear solution was treated with a small quantity of sodium bisulphite, cautiously neutralized with acetic acid, and evaporated to dryness. Extraction of the residue with isopropyl alcohol yielded, after evaporation, a 0.1 g. of the waxy product of Example V, soluble in water and benzene, but insoluble in hexane.

Example VII Ethomeen S/60 is a commercially available amine structurally similar to the amine of Example V but where R=the soy mixture detailed in the specification. A 100 g. portion of Ethomeen S/ 60 was added to a mixture of 800 ml. of Solv D and 200 ml. of chloroform and treated with chloramine according to the procedures described in the previous examples. The reaction mixture was decanted free of solvent and added to an equal volume of acetone. This mixture was stirred and filtered from ammonium chloride. The acetone soluble portion of the precipitate and the residue obtained on evaporation of the filtrate appeared as an ivory paste. This paste was purified by washing with isopropyl alcohol. The washing procedure fractionated the product to some extent into more saturated and less saturated portions. The pasty unfractionated material, 1-soy-1,1-bis- (polyethoxyethyl)hydrazinium chloride, runs clear at about 90 C. and it is very soluble in water. ous solution of this material when treated'with aqueous sodium sulfathiazole gives a precipitate, which when separated, appears as mats of fine lustrous plates melting at about 171172 0 They are poorly soluble in cold water and dispersible hot.

. averaging was added in a 100 g. portion to one liter of Solv D.

This solution was treated for 1 hour with 0.00656 .mol

of chloramine per minute. .The ammonium chloride An aqueoil was washed with small portions of kerosene and was filtered off and filtrate concentrated in vacuo to 250 ml. of a. paraffinic solvent (kerosene), to get two Thebottom layer was. treated with an equal layers. volume of keroseneand reseparated. The material was vacuum stripped in a nitrogen atmosphere to give 78.8 g. of 1-octadecyl-1,1-bis-(fl-hydroxytetraethoxyethyl) hydrazinium chloride. The product was slightly thicker and darker than that'of'Example II, It; forms yellow gums when treated with potassium hexafluorophosphate and potassium mercuriiodi'de.

Example V Bis-*(Z-ethylliexyl)aminoethanol" J (ciatca nm aicmqa 01H; 100 ml. was treated with 4 molar equivalents of chloramine. After all the chloramine had reacted, the material was filtered. The filtrate contained chloride, in-

dicating the formation of solvent-soluble hydrazinium chloride. The filtrate was then diluted with 1000 ml. of xylene and exhaustively chloraminated with intermittent filtrations to remove ammonium chloride. The filtrate was finally stripped of; solvent, washed well.v with hexane anda minimum quantity of water, The residue thus obtained appeared as a yellow oil about 88% pure 1,1-1

, Example Ethomeeen 2C/;11 is a commerciallyavailable mixture of amines where C denotes coco asdescribed in the specification supra, and 11 denotes anjaverage of 1 C H O per molecule. A 50 g. portion of EthomeenlC/dl was dissolved in 950 ml. of Solv D. This solution wassuba jected to the chloramine stream from the generator at a rate of 0.0045 mole of chloramine per minute over a period of ninety minutes. After standing overnight, a relatively small quantity of ammonium chloride precipitate formed. The yellow filtrate was evacuated in vacuo, washed well with hexane and vacuum dried to give a very thick yellow-brown oil. This novel oil was dispersible in water and soluble in chloroform. It was purified to a thick clear yellowish paste of 1,1-dicoco-l- (2-hydroxyethyl)hydrazinium chloride which ran clear at about 69 C.

Example XI A branched chain fatty amine mixture containing homologs of the formula C I-I NHC H OH isavailable commercially under the trade-name of Priminox 43. It is a dark viscous liquid which the manufacturer states has a neutralization equivalent of 405 (calculated for C H NO,397).

Five g. of this product was refluxed with 50 ml. of formalin and 50 ml. of 90% formic acid for 6 hours,

allowed to cool and brought to pH 9.0 by the slow addi- 7 tion of 20% aqueous NaOH at 1520 C. On standing 6 g. of a dark oil similar in appearance to the starting amine appeared as the upper layer. was taken up in ml. of chloroform, washed once with cold water, dried over magnesium sulfate, chloraminated with approximately 5 g. of chloramine and filtered after standing overnight. Evaporation of the filtrate gave a thick dark oil containing 5.2% C1". The

vacuum dried to constant weight at 35 C. yielding 3.8 g, of a thick oil containing 6.2% 01-. The product, 1-

The separated oil '11 methyl-l- (2-hydroxyethyl) .-l-alkylhydrazinium chloride; a mixture of homologs of the general formula To further demonstrate the utility of some of our novel compounds rat repellency tests were conducted. These tests comprise isolating -a specimen rat for a period of 96 hours with two food containers, one of which contains twenty g. of untreated food and the other 20 g. of food treated with 2% by weight of a material to be tested as a rat repellent. Repellency is measured by means of a Repellency Index, K, obtained by using the formula shown below:

In the above formula T is equal to the daily consumption of treated food, U isequal to the daily consumption of untreated food, the subscripts of l, 2, 3 and 4 refer to the four days during the testing period, X is the weight of untreated food remaining after the fourth day and W is the body weight of the animal in kilograms. A value of 100 represents complete repellency. Samples of our novel soy-bis-(hydroxypolyethoxyethyl)hydrazinium chloride and tallowbis-(hydroxysesquiethoxyethyl)hydrazinium chloride were used as the treating material in the tests described hereabove. The first of these compounds gave a repellency index of 93 and the second a repellency index of 92. These results clearly show our novel compounds to be efiective as rat repellents.

I claim:

1. As a new chemical compound 1,1-bis-(2-hydroxyethyl)-l-octadecylhydrazinium chloride.

2. As a new chemical compound 1,1-bis-(hydroxypolyethoxyethyl)-1-octadecyldienylhydrazinium chloride.

3. As a new chemical compound l,l-bis-(2-ethylhexyl)- I-(Z-hydroxyethyDh'ydrazinium chloride.

- 4. As a new chemical compound 1,l-bis-octadecyl-l- (hydroxypolyethoxyethyl hydrazinium chloride.

5'. As a new chemical compound l-benzyl-l-(Z-hydroxyethyD-l-octadecylhydrazinium chloride.

6. New chemical compounds having'the' general forwherein R is a member selected from the group consisting of alkyl, alkenyl and alkadienyl radicals containing 8 to 24 carbon atoms; R is a member selected from the group consisting of hydroxyloweralkyl, hydroxyloweralkoxyloweralkyl and hydroxypolyloweralkoxyloweralkyl; R is a member selected from the group consisting of hydroxyloweralkyl, hydroxyloweralkoxyloweralkyl, hydroxypolyloweralkoxyloweralkyl, benzyl, halobenzyl, and alkyl, alkenyl and alkadienyl radicals containing 1 to 24 carbon atoms; A is a member selected from the group consisting of halide, sulfate phosphate, nitrate and acetate. 7. Componnds according to claim 6 wherein R is an alkyl radical containing 8 to 24- carbon atoms, R and R" are hydroxyloweralkyl and A is halide.

8. Compounds according to claim 6 wherein R is an alkenyl radical containing 8 to 24 carbon atoms, R and R are hydroxypolyloweralkoxyloweralkyl and A is halide.

9. Compounds according to claim 6 wherein R is an alkyl radical containing 8 to 24 carbon atoms, R is hydroxyloweralkyl, R is an alkyl radical containing 1 to 24 carbon atoms and A is halide.

10. Compounds according to claim 6 wherein R is an alkyl radical containing 8 to 24 carbon atoms, R is hydroxypolyloweralkoxyloweralkyl, R is an alkyl radical containing 1 to 24 carbon atoms and A is halide.

M 11. Compounds according to claim 6 wherein R is an alkyl radical containing 8 to 24 carbon atoms, R is hydroxyloweralkyl, R is benzyl and A is halide.

No references cited. 

5. AS A NEW CHEMICAL COMPOUND 1-BENZYL-1-(2-HYDROXYETHYL)-1-OCTADECYLHDRAZINIUM CHLORIDE 